Method for emitting fluorescent light using fluorescent quinazolones



r 3,269,955 C6 Patented August 30, 1966 No Drawing. Original application May 10, 1963, Ser. No. 279,631, now Patent No. 3,169,129, dated Feb. 9, 1965. Divided and this application June 11, 1964, Ser. No.

13 Claims. '(Cl. 252-301.2)

This application is a division of application Serial Number 279,631, filed May 10, 1963, now US. Patent 3,169,129.

This invention relates to the emission of visible light from objects exposed to radiation from a suitable source of exciting energy such as ultraviolet light. More par ticularly, it deals with surfaces or layers capable of being thus excited to emit visible light. Still more specifically, it is concerned with such light-emitting surfaces which comprise in a solid form a compound characterized by having very little or no visible color in white light and having superior stability to deterioration when exposed to ultraviolet irradiation.

Primarily, the present invention is concerned with such compounds represented by the formula:

wherein, R R R and R each represent hydrogen or a substituent such as halogen, hydroxyl, an alkyl or alkoxy of 1-4 carbons; and R represents hydrogen or an alkyl of 1-4 carbons. Within this group of compounds, a preferred subclass is that in which R is hydroxyl and the other Rs are as defined above. Accordingly, they are used herein for the purposes of primary illustration.

Fluorescence, or the emission by certain materials (phosphors) of light energy (luminescence) of one wavelength when irradiated by exciting light of a different wavelength, usually lower, has been well-known for many years. Also well-known is the phenomenon of phosphoresence exhibited by some materials, i.e., persistence of the luminescence after removal of the source of exciting radiation. In the past, various practical applications of fluorescent phenomena have been proposed with varying degrees of success.

Usually these involved irradiation with ultraviolet light, resulting in illumination by emission of visible light at longer wavelengths. For such purposes, inorganic phosphors have had quite wide application. In general, however, organic materials have been found applicable only in very few instances, being limited, in part, by a lower degree of stability than inorganic materials under the types of irradiation encountered. Moreover, most of the applicable compounds have been dyes such as rhodamine, which are self-colored. This is definitely undersirable for many potential applications.

Fluorescence is also involved in the field of brighteners or optical bleaches. Here, organic materials have been applied with great success on a broad commercial scale. However, organic materials found useful for such purposes have not been found generally useful for fluorescent illuminating purposes. In large part this is due to minimal fluorescence of the material in the solid state and to relative instability and decided degradation under continued exposure to exciting radiation in the ultraviolet range.

In the illuminating field, as noted above, some limited use of organic materials as fluores'cers has been proposed. One such is in application as screens, not as a major source of illumination but for purposes of shading or modifying the color or tone of light from some other source. Such a screen may be used to improve the spectra of light sources deficient in one or more spectral color elements to a more desirable spectrum or shade of light.

One example of such application is found in US. Patent No. 1,150,118. Therein, a fluorescent screen or surface using an organic material such as a rhodamine dye is used to impart an improved color value to illumination emitted from a mercury vapor lamp, i.e., to produce a whiter light closer to daylight than is the greenish-blue tone of light normally produced by a mercury vapor lamp. Thus, such a light transfonming screen or reflector is useful for converting some of the rays of the light source to light of a more desirable wave-length. Such sources could be mercury vapor lamps or tungsten or carbon filament lamps. Other illustrations are found for example in US. Patents Nos. 2,177,701 and 2,149,992. Fluorescence phenomena have also been applied to coating compositions, for example, in uses involving pigment compositions.

However, one of the principal deterents to wider use of organic materials in fluorescent screens or films still remains the relative instability encountered on prolonged exposure to exciting ultraviolet light and/ or the relatively weak fluorescence in the solid state. Thus, for example, many of the compounds useful as brighteners or optical bleaches do show the desired shades of fluorescence but lack sufiicient stability against deterioration when exposed to ultraviolet exciting light for extended periods. Moreover, many fiuoresce only weakly or imperceptably in the solid state.

Consequently, in illumination, and in related arts, there remains a definite need for suitable fluorescent low-cost, organic materials. Such materials should exhibit little or no visible color in white light. Under ultraviolet irradiation in the solid state they should fluoresce strongly in desirable shades. They should be adequately stable to the effect of such irradiation as well as to the effect of heat for extended periods.

Such materials would be extremely useful for a variety of applications, especially in the illumination field or in other fields where fluorescence is desirable. Thus, in the illumination field, screens or panels giving various shades of light under excitation would be useful, not only for general illumination but to produce novel or theatrical effects, signs, coating compositions, fluorescent finishes, fluorescent lamps and the like.

It is, therefore, the principal object of the present invention to provide such organic materials. In the present invention this object has been accomplished to a surprisingly successful degree by the discovery and use of the compounds of Formulae I which were discussed above. In accordance with the present invention, it has been found that colorless or nearly colorless compounds so defined show strong fluorescence in the solid state, give off desirable shades of visible light when irradiated with ultraviolet light; have a high degree of stability to the effect of heat; and do not excessively deteriorate or lose fluorescence during exposure to ultraviolet light, even over prolonged periods.

Accordingly, these compounds are highly useful in applications requiring emission of visible light on exposure to ultraviolet light. They may be formulated successfully in solid form in screens, films, coatings, and the like to obtain the fluorescent effects desired. Discovery of the fluorescent properties and stability of these compounds .in the solid state and their applicability for fluorescent purposes was completely unpredictable and unexpected.

It is an advantage of compounds used in the present invention that they may be prepared by known general methods of synthesis. Among such methods, the following have been found convenient.

Method A.Reaction of an aroyl anilide with urethane (ethyl ester of aminoformic acid) in the presence of phosphorus pentoxide. This may be illustrated by the following reaction scheme:

Although yields by this method generally are not as high as might be desired, this method often is convenient. It affords a procedure for obtaining various substituted derivatives from more readily available or more easily prepared starting materials. Thus, by choosing appropriately substituted anilides, the desired substituted quinazolones may be prepared. Illustrative aroyl anilides which may be used in this method include: p-anisanilide 4'-butyl-p-anisanilide 4'-chloro-p-anisanilide 4'-bromo-p-anisanilide 4-methyl-anisanilide benzanilide 4'-methylbenzanilide 4-chlorobenzanilide 2-chlorobenzanilide p-benzanisidide p-anis-o-anisidide p-anis-p-anisidide 4,4-dichlorobenzanilide 2,4'-dichlorobenzanilide 2-methyl-4'-chlorobenzanilide 2-methyl-4'-butylbenzanilide Method B.Reaction of an anthranilamide with an aromatic aldehyde by heating in the presence of a solvent, such as ethanol, to give an anil type which then is ring closed to a dihydroquinazolone in the presence of canstic; the dihydroquinazolone then being oxidized to the corresponding quinazolone. This may be illustrated by the following reaction scheme:

Nm (Eton) N=CHR (RCHO) ooNrn coNm ii N CHR oxidize I R N11 NH This procedure also may be used to obtain substituted derivatives by using appropriately substituted starting benzaldehyde o-anisaldehyde p-anisaldehyde m-anisaldehyde 2,4-dimethoxybenzaldehyde 2-chlorobenzaldehyde 4-chlorobenzaldehyde 4-bromobenzaldehyde Method C.By cyclization of N-aroyl anthranilamides under alkaline conditions as illustrated in the following reaction scheme:

C ONHz Here again substituted derivatives may be prepared by having appropriate substituents in the starting materials.

Various known methods are available for evaluation of these compounds as organic fluorescent materials; for example determination of the color and strength of fluorescence; the stability on irradiation; and the like. Stability, however, may vary appreciably, depending on the test conditions. For example, in solution some compounds may be relatively unstable yet in the solid state show extremely high stability. Thus, for example, when certain compounds are incorporated in cellulose acetate and exposed to UV light in a Fade-Ometer they may show stability of seemingly low order. However, the same compound in the solid state, as in the form of a thin film deposited from solution, in many instances shows a very high degree of stability Different compounds of the present invention when exposed to UV light show fluorescence in various colors, As stated above, they may show varying degrees of stability. Also as noted above, preferred compounds of the invention, especially as to stability and as to intensity and shade of emitted visible light when exposed to UV are those of Formula I in which R is an ortho-hydroxy substituent. Among these, 2-(2-hydroxyphenyl)-4(3)-quinazolone is especially desirable because of its shade of fluorescent light and high stability.

Compounds of the invention may be used in a very large variety of applications, based on their fluorescence and stability properties. Thus, for example, they may be used in lighting panels; in various types of plastic compositions; in inks, paints and the like; or in any application applied to a surface or in a film for emission of visible light upon exposure to UV light. A specific application of interest is the use of a fluorescent compound of the invention in printing inks, paints, enamels and other surface coating compositions to produce a composition which has one appearance by daylight and a completely different appearance or color under UV or black light. Such effects are useful for various decorative uses and for purposes of identification or security.

As fluorescers, compounds of the invention absorb UV light and by virtue of this property also have some application as protective agents in plastic compositions, that is as UV absorbers. In such cases, it is the UV-absorbing property which is important rather than conversion of incident UV light to emitted visible light.

This invention will be further illustrated in conjunction with the following examples. Therein, unless otherwise noted, all parts and percentages are by weight and temperatures are in degrees Centigrade. Preparation of the 4(3)-quinazolones is illustrated by Examples 1-37 inclusive. Preparation of the preferred 2-(2-hydroxylphenyl)-4(3)-quinazolones which are believed to be new I? J compounds is illustrated in Examples 22-37. Properties and uses of these compounds are shown in the remaining examples.

EXAMPLE 1 Preparation of 2-(4-meth0xyphenyl)-4(3)-quinaz0l0ne EXAMPLES 2-15 The procedure of Method A as shown in Example 1 is repeated, substituting for the p-anisanilide equimolar amounts of various anilides and anisidides. Starting materials and resultant -4(3)-quinazolones are shown in the following table.

TABLE I Starting Material -4(3)-quinazolone Benzanilide p-B enzanisidide. p-Anis-p-anisidide 4-butyl-p-anisidide p-Anis-o-anisidide 4-chlorobenzanilide 2-eh1or0benzanilide 3 ch1orobenzani1ide 4-ethylbenzanilide 4-chloro-4-butoxybenzanilide. 4-ethoxy-2-ethylbenzanilide. 4-bromo-3-ehlorobenzanilide 2'-propoxy-3,5-dibromobenz anill Q-phenyl G-methoxy-Z-phenyl fi-methoxy-Z-(Qmethoxyphenyl) 6-butyl-2-(4rneth0xy-phenyl) 8-methoxy-2-(4-methoxyphenyl) fi-chloro-Z-phenyl 8-chloro-2-phenyl 2-(3-chlorophenyl) 2-(4-ethylphenyl) G-ehloro-Z-(4-butoxyphenyl) fi-ethoxy-2-(2-ethylphenyl) 6-br0mo-2-(B-ehloropbenyl) 8-propoxy-2-(3,5-dibromophenyl) 6-ethyl-2-(i-hydroxyphenyl) e. 4-ethyl-4-hydroxybenzanilide EXAMPLE 16 2-phenyl-4 (3 -quinaz0 l0ne As illustrative of Method B, a solution containing 204 g. of anthranilamide and 2 ml. of conc. HCl in 800 ml. of ethanol is treated with 160 g. of benzaldehyde followed by heating for minutes. Ten percent aqueous sodium hydroxide (2.7 liters) is then added and the mixture is heated to distill off the ethanol. The crude product is collected by filtration and recrystallized from ethanol; M.P. 234235 C. The resultant dihydro compound (100 'g.) is slurried in 2.5 liters of 2.5% aqueous caustic and heated to C. Sodium hypochlorite (450 ml. 10% solution) is gradually added While heating to 65 C. in one hour. The reaction mixture is clarified hot, cooled and acidified with acetic acid. The product is collected, washed with water and dried; M.P. 240-241 C.

EXAMPLES 17-21 Using Method B as exemplified in Example 16, substituting for the benzaldehyde equivalent amounts of oanisaldehyde and other aldehyde starting materials, the products shown in the following Table II are obtained.

TABLE II IIJIx. Starting Material -4(3)-quinazoione 17 o-Anisaldehyde 2-(2-meth0xyphenyl) 18 p.Iolualdehyde 2-(4-methy1phenyl) 19 4-chlorobenzaldehyde... 2-(4-ch10rophenyl) 20 2,4-dichlorobenzaldehyde 2-(2,4-dichlorophenyl) 21"-.. Milthgxy-B-methoxybenzalde- 2-(4-ethoxy-3-methoxyphenyl) In the following examples preparation and utilization of the preferred subclass of compounds of Formula I are illustrated. As there noted, these compounds are within Formula I but have the structure R R R and R are as defined above for Formula I. In most cases R and R will be hydrogen.

EXAMPLE 22 2-(2-hydr0xyphenyl)-4 (3 )-quinazolone NH OH A mixture of 648 g. salicylic acid, 580 g. thionyl chloride, and 3 ml. of pyridine is heated four hours at 40 C. The excess SOCl is removed by vacuum distillation. This as is acid chloride is added dropwise to a stirred refluxing mixture of 500 g. anthranilamide, 635 g. of K CO and 5.5 liters of dry ether. After refluxing 3 hours the other is removed by distillation and the product washed with water. This is slurried in 14 liters of 5% NaOH and boiled for one hour. After cooling the solution was neutralized with acetic acid and the product was isolated by filtration; 634 g., M.P. 280284 C. This is recrystallized from acetic acid to give a light yellow solid, M.P. 297-298 C.

EXAMPLE 23 The procedure of Example 22 is employed, substituting 4-ethoxysa'licylic acid in place of salicyclic acid, to synthesize 2-(4-ethoxy-2-hydroxyphenyl 4(3) quinazoline.

EXAMPLE 24 2- 4-chl0r0-2-hydr0xyphenyl -4 (3 -qwinazol0ne 4-chlorosalicylic acid (86.3 g., 0.5 m.), thionyl chloride (150 cc.) and pyridine (0.5 cc.) are stirred for 3 hours at 3040 C. Excess SOCl is removed by vacuum distillation below 40 C. The resulting acid chloride is added over a period of one-half hour to a mixture of 55 g. of anthranilamide and 70 g. of anhydrous potassium carbonate in 200 cc. of benzene and 450 g. of diethyl ether. The mixture is stirred overnight and then treated with 1400 cc. of 5% aqueous sodium hydroxide. The reaction mixture is heated to C. for one hour, cooled and neutralized with acetic acid. The product is collected by filtration and recrystallized from phenol. It shows a melting point of 345 7 C EXAMPLE 2- (2-hydroxy-3-methylphenyl) -4 (3 -qm'naz0lone Seventy-six g. (0.5 m.) of 3-methylsalicylic acid is used in place of the 4-chlorosa-licylic acid in Example 24. The product, recrystallized from ethanol, shows a melting point of 2535 C.

EXAMPLE 26 2- (3,5 -dichlor0-2-hydroxyph enyl -4 (3 -quinaz0lone One-half mol (103.5 g.) of 3.5-dichlorosalicylic acid is used in place of the 4chlorosalicylic acid in Example 24. The desired product is purified from methyl Cellosolve.

EXAMPLE 27 One-half mol (148 g.) of 3,5-dibromo salicylic acid is employed in place of the 4-chlorosalicylic acid in Example 24. The product, 2-(3,5-dibromo-2-hydroxyphenyl)-4(3)-quinazolone, is recrystallized from pyridine.

EXAMPLE 28 stituting the appropriate starting acid, the compounds shown in the following Table III are prepared.

TABLE III Ex. No.2 -4(3)-quinazolone 29 2-(2-hydroxy-4-methoxyphenyl) 30 2-(2,4-dihydroxyphenyl) 31 2-(2-hydroxy-4-butoxyphenyl) 32 2-(2-hydroxy-5-butylphenyl) 33 2-(2-hydroxy-5-iodophenyl) It is also within the scope of the present invention to convert the 2-hydroxyphenyl compounds into other derivatives by further reaction of the hydroxyl group. This is shown in the following examples.

EXAMPLE 34 2- (Z-carbelhoxyoxyphenyl -4 (3 -quinaz0l0ne 2-(2-hydroxyphenyl)-4(3) quinazolone (71.5 g., 0.3 m.) and sodium hydroxide (13.2 g., 0.3 m.) in 1000 cc. of water is treated with 38.5 g. (0.33 m.) of ethyl chlorocarbonate. The reaction is complete after one-half hour and the product is collected by filtration. The product is recrystallized several times from a 3:1 mixture of toluene and methylcyclohexane, M.P. 1456 C.

EXAMPLE 35 1) 2-(2-hydr0xyphenyl-3-methyl-4 (3 -quinaz0l0ne (2) 2- 2-methoxyphenyl-3-methyl-4 (3 -quz'nazol0ne 2-(2-hydroxyphenyl)-4(3)-quinazolone (59.5 g., 0.25 m.), sodium hydroxide (30 g.) and potassium carbonate (10 g.) are dissolved in 1700 cc. of water and treated with 140 cc. of dimethyl sulfate and 120 cc. of 50% aqueous sodium hydroxide concurrently. Solid was filtered OE and recrystallized from ethanol. The product analyzed for the Z-methoxyphenyl derivative.

The alkaline filtrate from above is acidified and solid collected. Recrystallized from ethanol, the product analyzed correctly for the 2-hydroxyphenyl derivative.

EXAMPLE 36 A mixture of 2-(2-hydroxyphenyl)-4(3) quinazolone 11.9 g. (.05 m.) and 7.6 g., (.06 m.) of butyl bromide in 200 ml. of acetone containing 7.9 g. (.05 m.) of anhydrous potassium carbonate is refluxed for 12 hours. The reaction mixture is then added to Water and the solid product collected. The solid is extracted with alcoholic aqueous sodium hydroxide and the extract is neutralized with dilute hydrochloric acid. The product, 3-butyl-2- (Z-hydroxyphenyl) 4(3) quinazolone, is collected and purified.

EXAMPLE 37 The above procedure is used to prepare: 3-ethyl-2-(2- hydroxy-3,S-dichlorophenyl)-4(3 -quinazolone from ethyl iodide and 2-(2-hydroxy 3,5 dichlorophenyl) 4 (3)- quinazolone and to prepare a 3-propyl-2-(2-hydroxy-3- methylphenyl)-4(3 )-quinazolone from 2-(2 hydroxy 3- methylphenyl)-4(3)-quinazolone and p'ropyl bromide.

As noted above, in the solid state, compounds of this invention exhibit a wide range of fluorescent color. Typical illustrations of fluorescent color when exposed to UV radiation (3650 A.) in the solid state are shown in the following table.

TABLE IV -4(3 -quinazolone: Color of fluorescence 2-phenyl Light violet. 2-(4-methoxyp'henyl) Blue white. 2-phenyl-6-methoxy Blue white. 2-phenyl-6-chloro Violet. 2-(4-methoxyphenyl)-6-butyl Blue white. 2-(4-methoxyphenyl)-6-methoxy Blue white. 2-(4-methoxyphenyl)-8-methoxy Blue white. 2-(2methoxyphenyl) Light yellowish green. 2-(4-ethoxy-3-methoxyphenyl) White. 2-(Z-methoxyphenyl)-3-methyl Light violet. 2-(2-hydroxyphenyl) Green. 2-(2-hydrovy-4-ethoxyphenyl) Bluish white. 2-(2-hydroxy-4-chlorophenyl) Green. 2-(2-hydroxy-3-methylphenyl) Yellow green. 2-(2-hydroxy-3,5-dichloropher1yl) Yellow. 2-(2-hydroxy-5-chlorophenyl) Yellow green. 2-(2-hydroxyphenyl)-3-methyl Green.

The 2-(2-hydroxyaryl)-4(3)-quinazoloncs had intensities of fluorescence vastly superior to the derivatives not possessing Z-hy-droxyl structures.

EXAMPLE 3 8 Illustrative 4(3)-quinazolones were examined in sodium chloride wafers to determine the intensity of luminescence and light stability as shown by the percent luminescence remaining after prolonged exposure to UV light. Wafers containing 0.2% luminescer are prepared by grindthe luminescer with the NaCl in a porcelain mortar until a fine powder having uniform luminescence under a black light is obtained. One or two grams of this powdered mixture is sintered in a 1.750-inch diameter die, at a. pressure of 150,000 lb./in. to form a transparent to translucent wafer. The wafer is then mounted on a 2 x 2 inch optical glass slide with black, pressure-sensitive plastic tape. Observations are made on the color of luminescence under black light. The intensity of fluorescence of each wafer is determined using a Galvanek-Morrison fluorimeter. Fluorescence is compared to a blue fluorescing plastic sheet which is used as a standard for comparative purposes and is arbitrarily assigned the fluorescent strength of 1.0. In order to allow the intensity of luminescence to stabilize, the first hours of exposure are considered as a break-in period. The waters are aged in a fluorescent sun lamp black light exposure unit (FSBL) and the change of fluorescent intensity with time of exposure is determined. In the following Table IV, illustrative results obtained with one gram wafers containing various quinazolones after 3380 hours exposure are given. Results obtained with 4(3-)quinazolones that do not have the Z-hydroxy substituent are first shown; followed by those for the new Z-hydroxy compounds of the present invention.

TABLE IV Color of Relatve Percent -4(3)-quinazolone Lumines- Initial Luminescence Intensity ence After Exposure 2-(4-methoxyphenyl) Blue 0. 24 24 2-plienyl Dull blue 0.10 27 fi-methoxy-z-phenyl -.do 0. 05 28 2-(2 hydroxy-4-ethoxypheiiyl) Aqua 0.84 65 2-(2-hydroxyphenyl) Green 0.86 73 In the following Table V typical results obtained using two gram wafers exposed for 3100 hours are shown.

TABLE V Color of Relative Pereeu -4(3)-quinazolone Lumiiies- Initial Luminesoence Intensity ence After Exposure 2-plienyl Blue. 0.36 47 fi-methoxy-Z-phenyl. Dull blue 0. 50 41 fi-chloroQ-phenyl 0. 05 (2) 6-butyl-2-(metlioxy-plienyl 0. 19 38 6-n1ethoxy-2-(4-metlioxy- 0. 24 52 phenyl). 8-methoxy-2-(-4-methoxy- 0. 46 26 phenyl). 2-(2-methoxyphenyl) White 0. 67 52 2-(2-hydroxyphenyl) Green 0. 91 83 2-(2-hydroxy-4-ethoxy- Blue white 1. I 74 pheiiyl).

In the following Table VI illustrative results on two gram wafers after 4700 hours exposure are shown.

TABLE VI Color of Relative Percent -4(3)-quiiiazolone Lumines- Initial LllIIllllGS- cence Intensity ence After Exposure 2-(2-liydroxyphenyl) Gree11 0.91 71 2-(4-methoxyphenyl) Dull white.v 0.33 23 As can be seen from Tables IV, V and VI, the intensity of luminescence and light stability of the 2-(2-hydroxyaryl)-quinazolones are markedly superior.

EXAMPLE 39 The 2-hydroxyphenyl derivative of Example 22 was evaluated as the fluorescer in (1) a colorless unpigmented by daylight and a diiferent appearance or color of strong intensity under UV light. Preparations of the inks and illustnative results are shown as follows:

(1) Unpigmented ink Colorless inks, luminescent green under ultraviolet light, were prepared by milling differing amounts of the compound of Example 22 into a commercial ink vehicle (IPI K-592 Vaposet). Drawdowns were made from this ink and samples were subjected to black light exposure. The intensity of fluoresence of each drawdo-wn was determined (by the procedure of Example 37) and the hours of exposure necessary to decrease the luminescence to a relative intensity of 0.01 were then determined. Illustrative results are shown in Table VII below.

TABLE VII Cone, Relative percent Initial Hours Exposure Intensity (2) Pigmented inks The compound was incorporated by the same procedure, i.e., by milling into samples of the same commercial ink vehicle pigmented with the following commercial pigments: (A) Litho Red; (B) Chrome Green; and (C) Iron Blue respectively. Illustrative results are Samples of molybdate orange and chrome green type T rotogravure inks containing 5% of the compounds of Example 22 and of Example 23 were prepared by shot milling the additives into the wet inks using a two-roll blending machine. A blending time of 24 hours was allowed. Dra wdowns were made and examined under ink composition; and (2) in colored pigmented ink comvisible and black light. positions. The result-ant coatings have one appearance Observations are as recorded in Table IX.

TABLE IX Additive Black Light Ink Paper Stock Fluorescence Visual Color Color Color Percent Ex. N0.

Roto-orange Green tint 0 Noi1e Reddishorange.

5 22 Yellow Do.

5 23 Dull green Do.

Roto orange White bond 0 Very dull red Do. 5 22 Tan Do,

5 23 Brown D0.

Rom-green Green tint 0 Very dull green- Green.

ish-gray.

5 22 Bright green D0.

5 23 Bluish-green. Do.

Rota-green White bond 0 Very dull greeii- Do.

ish-gray. 5 22 Green Do. 5 23 Bluish-green Do.

1 Brightened.

Two samples of fluorescent type T rotogravure ink were prepared by shot milling the following formulations on a 2-roll blender for 24 hours.

Parts Formulation A:

Type T vehicle 70 Chrome Green Luminescer (Ex. 13) 15 Formulation B:

Type T vehicle 6O Molybdate Orange Luminescer (Ex. 13) 20 A drawdown of Formula A roto ink exhibited a strong green fluorescence while a drawdown of Formula B exhibited a strong yellow fluorescence under the black light.

EXAMPLE 41 2-(2-hydroxyphenyl) 4(3)-quinazolone was incorporated at concentration into a commercial black letterpress ink. A three-roll ink mill was used to incorporate the additive into the ink sample. Six passes were made at 500 pounds yielding an ink giving a 7+ on a Hegm-an gauge. A drawdown showed a strong green luminescence under black light.

Samples of letterpress black ink were similarly prepared with several standard commercial inorganic luminescencers such as zinc sulfide or zinc cadmium sulfide. The drawdowns of these exhibited only faint luminescence under black light.

Samples of letterpress black ink were similarly prepared with compounds of Examples 16, 18 and 19. The drawdowns exhibit strong yellow green, yellow and yellow green luminescence respectively, under block light.

EXAMPLE 42 Two and one-half grams of compound of Example 22 is thoroughly mixed into 7.5 g. of a white-paint having the following formulation:

Percent Titanium dioxide 11.0 Titanium calcium 30.0 Zinc oxide 2.4 Linseed soya-alkyd resin 23.9 Mineral spirits 30.4 Driers 2.3

A drawdown is prepared which has intense green fluorescence under black light.

EXAMPLE 43 Seven and one-half grams of a varnish consisting of 50% linseed soya ester gum alkyd resin in 50% petroleum thinner and driers is treated with 2.5 g. of compound of Example 22. A drawdown is prepared which is essentially colorless and which luminesces bright green under black light.

EXAMPLE 44 To 7.5 g. of a pastel green paint having the following formulation:

is added 2.5 g. of compound of Example 22 and 5 g. of water. A drawdown has a pastel green visible color and a strong green luminescence under black light.

EXAMPLE 45 2-(2-hydroxyphenyl)-4(3 -quinazo1one is incorporated at 5% by weight into a polyvinyl chloride homopolymer formation of parts Geon 103 EP, 2 parts Thermolite 31, and 0.5 part stearic acid. A 2-roll rubber mill is used for incorporation. The mill rolls are gapped at 0.010 inch and heated at C. The polymer formulation dry blended with the 2-(2-hydroxyphenyl)-4(3)- quinazolone is allowed to band and is milled for 5 minutes. The polymer is again banded and removed from the mill as a sheet. Under black light the polymer containing 5% 2-(2-'hydroxyphenyl)-4(3)-quinazolone emits a strong green luminescence.

EXAMPLE 46 2-(2-hydroxyphenyl)-4(3)-quinazolone is incorporated at 5% by weight into Goodrich Abson ABS polymer using procedure described in Example 45. Under black light the polymer emits a strong green luminescence.

EXAMPLE 47 2-(2-hydroxyphenyl)-4(3)-quinazolone is incorporated at 5% by Weight into Hercules Profax 6501 polypropylene using procedure described in Example 45. Under black light polymer emits a strong green luminescence.

EXAMPLE 48 2-(2-hydroxy-4-ethoxyphenyl)-4(3)-quinazolone is incorporated into the PVC homopolymer formulation described in Example 45, using the procedure of Example 45. The polymer under black light emits a strong blue luminescence.

We claim:

1. A surface adapted to fluoresce during exposure to radiation from a source of ultraviolet light; said surface having as its fluorescent component a 4(3)-quinazolone of the formula:

wherein R R R and R are selected from the group consisting of hydrogen, hydroxyl, halogen and l-4 carbon alkyl and alkoxy; R is selected from the group consisting of hydrogen and alkyl of 1-4 carbons; said quinazolone being further characterized by having substantially no visible self-color in daylight and having in the solid state a high stability when exposed to ultraviolet light for long periods.

2. A surface according to claim 1 in which said quinazolone is in the solid state.

3. A surface according to claim 2 in which said quinazolone is distributed over a supporting material and bonded thereto by a substantially colorless bonding material.

4. A surface according to claim 2 in which said bonding material is self-colored.

5. A surface according to claim 2 in which said quinazolone is distributed through a thin layer of material in supported contact with a supporting layer.

6. A surface according to claim 1 wherein R is hydroxyl and R and R are hydrogen.

7. A method for causing a surface to fluoresce during exposure to radiation from a source of ultraviolet light; which comprises forming a surface consisting essentially of a quinazolone in the solid state, said quinazolone having the formula:

wherein R R R and R are selected from the group consisting of hydrogen, hydroxyl, halogen and 1-4 carbon alkyl and alkoxy; R is selected from the group consisting of hydrogen and alkyl of 1-4 carbons; said quinazolone being the fluorescent component of said surface, said quinazolone being further characterized by having substantially no visible self-color in daylight and having in the solid state a high stability when exposed to ultraviolet light; and exposing said surface to radiation from a source of ultraviolet light.

8. A method according to claim 7 wherein R and R are hydrogen and R is hydroxyl.

9. A luminescent printing composition consisting essentially of a liquid vehicle and a quinazolone of the formula:

wherein R R R and R are selected from the group consisting of hydrogen, hydroxyl, halogen and 1-4 carbon alkyl and alkoxy; R is selected from the group consisting of hydrogen and alkyl of 1-4 carbons; said quinazolone being present in a concentration suflicient to produce noticeable fluorescence and being further characterized by having substantially no visible self-color in daylight and having in the solid state a high stability when exposed to ultraviolet light and said liquid vehicle being a printing ink of the desired daylight color.

10. A luminescent printing composition consisting essentially of a liquid vehicle and a -4(3)-quinazolone selected from the group consisting of 2-(2-hydroxyphenyl)-, 2 (2 hydroxy-4-methoxyphenyl)-, 2-(3,5-dichloro 2 hydroxyphenyl) 2-(5-chloro-2-hydroxyphenyl)-, 2 (2 hydroxy 3-methylphenyl)- and 2(ethoxy-2- hydroxyp-henyl) 4(3) quinazolone; said liquid vehicle being a printing ink of the desired daylight color; the concentration of said quinazolone being sufficient to produce noticeable fluorescence upon exposure of the printing composition to ultraviolet light.

11. A shaped polymeric plastic article characterized by the fact that at least a part of one surface thereof contains a 4(3)-quinazolone in the solid state and in sufficient concentration to produce fluorescence under ultraviolet light, said quinazolone having the formula:

N-Rs R2 B3 wherein R R R and R are selected from the group consisting of hydrogen, hydroxy, halogen and 1-4 carbon alkyl and alkoxy; R is selected from the group consisting of hydrogen and alkyl of 14 carbons; said quinazolone being further characterized by having substantially no visible self-color in daylight and having in the solid state a high stability when exposed to ultraviolet light for long periods. 5 12. A liquid coating composition adapted to form an adherent fluorescent coating when deposited on a solid supporting surface, said composition containing as its fluorescent component an effective amount of a 4(3)- quinazolone in the solid state, said quinazolone having the formula:

wherein R R R and R are selected from the group consisting of hydrogen, hydroxyl, halogen and 1-4 carbon alkyl and alkoxy; R is selected from the group consisting of hydrogen and alkyl of 14 carbons; said quinazolone being further characterized by having substantially no visible self-color in daylight and having in the solid state a high stability when exposed to ultraviolet light for long periods.

13. A coated surface capable of fluorescing under ultraviolet light, said coating being formed by deposition on said surface of a liquid plastic composition containing an effective amount of a fluorescent 4(3)-quinazolone in the solid state, said quinazolone having the formula:

References Cited by the Examiner UNITED STATES PATENTS 2,837,485 6/1958 Siegrist 252301.2 2,910,495 10/1959 George 252-301.2 2,956,027 10/1960 Thompson 252-3012 2,992,221 7/1961 Petersen et al. 252-301.2 3,135,752 6/1964 Fields 252-301.2 3,201,406 8/1965 Mofiett 252--301.2

TOBIAS E. LEVOW, Primary Examiner.

R. D. EDMONDS, Assistant Examiner. 

1. A SURFACE ADAPTED TO FLUORESCE DURING EXPOSURE TO RADIATION FROM A SOURCE OF ULTRAVIOLET LIGHT; SAID SURFACE HAVING AS ITS FLUORESCENT COMPONENT A 4(3)-QUINAZOLONE OF THE FORMULA: 